한국환경과학회지 (Journal of Environmental Science International)

  • 제21권4호
  • /
  • Pages.421-435
  • /
  • 2012
  • /
  • 1225-4517(pISSN)
  • /
  • 2287-3503(eISSN)
한국환경과학회 (The Korean Environmental Sciences Society)
권호 표지
DOI QR코드

DOI QR Code

치환기를 가진 질소-산소(N2O2)계 네 자리 리간드의 합성과 중금속(II)이온 착화합물의 안정도상수 결정

Syntheses of Tetradentate Nitrogen-Oxygen(N2O2)) Ligands with Substituents and the Determination of Stability Constants of Their Heavy(II) Metal Complexes

  • 김선덕 (대구대학교 화학.응용화학과) ;
  • 설종민 (대구대학교 화학.응용화학과)
  • Kim, Sun-Deuk (Department of Chemistry and Applied Chemistry, Daegu University) ;
  • Seol, Jong-Min (Department of Chemistry and Applied Chemistry, Daegu University)
  • 투고 : 2011.11.30
  • 심사 : 2012.02.20
  • 발행 : 2012.04.30
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

Novel $N_2O_2$ tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the $para$ position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The proton dissociation constants ($logK_n{^H}$) of the phenol hydroxyl group and secondary amine of the synthesized $N_2O_2$ ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants ($log{\beta}_p$) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of $para$ Hammett substituent constants(${\delta}_p$). The stability constants($logK_{ML}$) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of $log{\beta}_p$ of the ligands. The order of the $logK_{ML}$ value of the each transition metal (II) ion was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II), which agreed well with that of Iriving-Williams series.

키워드

참고문헌

  1. Belaid, S., Djebbar, S., Benali-Baitich, O., Khan, M., G. Bouet, G., 2007, Complex formation between manganese, nickel, copper and a series of new ligands derived from N,N'-O-phenylenebis (salicylideneimine), C.R. Chime, 10, 568-572. https://doi.org/10.1016/j.crci.2006.09.012
  2. Cabbiness, D. K., Margerum, D. W., 1969, Macrocyclic effect on the stability of copper(II) tetramine complexes, J. Am. Chem. Soc., 91(5), 6540-6541 https://doi.org/10.1021/ja01051a091
  3. Canail, L., Sherrington, D. C., 1998, Utilisation of homogeneous of supported chiral metal(salen) complexes in asymmetric catalysis, Chem. Soc. Rev., 28, 85-83.
  4. Carlson, G. A., McReynolds, J. P., Verhoek, F. H., 1945, Equilibrium constant for the formation of ammonia complexes with certain metallic, J. Am. Chem. Soc., 67, 1334-1339. https://doi.org/10.1021/ja01224a036
  5. Chjo, K. H., Chjo, Y. K., Seo, S. S., Lee, S. J., 1991, Electrochemical properties of binuclear nickel(II) and copper(II) complexes with tetradentate schiff base in aprotic solvents(1), J. Kor. Chem. Soc., 35(1), 26-35.
  6. Chjo, K. H., Jeong, B. G., Kim, J. H., Jeon, S. W., Rim, C. P., Choi, Y. K., 1997, Synthesis and electrochemical Studies of Cu(II) and Ni(II) complexes with tetradentate schiff base ligands, Bull. Kor. Chem Soc., 18(8), 840-856.
  7. Coleman, W. M., 1981, Relationships between ligand carbon-13 chemical shifts and reduction potentials of Mn(III) complex, Inorg. Chim. Acta., 53, 191-193. https://doi.org/10.1016/S0020-1693(00)84792-1
  8. Fathi, S. A. M., Parinejad, M., Yaftian, M. R., 2008, Multidentate nitrogen/oxygen donor ionophores; their use as seletive extracting and mobile-carrier agents for copper(II) ions, Separation and Purification Technology, 64, 1-7. https://doi.org/10.1016/j.seppur.2008.09.003
  9. Gupta, K. C., Sutar, A. K., 2008, Catalytic of schiff base transition metal complexes, Coor. Chem. Rev., 252, 1420-1450. https://doi.org/10.1016/j.ccr.2007.09.005
  10. Jerry, M., 1968, Advanced organic chemistry: reaction, mechanisms and structure, McGraw Hill Book Company, New York, 238-245.
  11. Joseph, A., Bonadies, J. C., Carrano, C., 1985, Vanadium phenolates as metals for vanadium in biological Systems. 1. Synthesis, spectroscopy, and electrochemistry of vanadium complex of ethylenebis [(o-hydroxyphenyl) glycine] and its derivatives, J. Am. Chem. Soc., 108, 4088-4095.
  12. Katsuki, T., 1994, Catalytic asymmetric oxidations using optically active(aslen) manganees(III) complexes as catalysts, Coor. Chem. Rev., 140, 189-214.
  13. Kara, M., Alkan, M., 2001, Selective preconcentration, separation and speciation of ferric iron in different sample using N,N'-bis(2-hydroxy-5- bromobenzyl)1,2 diaminopropane, Talanta, 55, 415-423. https://doi.org/10.1016/S0039-9140(01)00443-X
  14. Kim, S. D., Jin, G. R., 2006, Syntheses of new $N_{2}O_{2}$ tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes, Analytical Science & Technokogy, 19(2), 131-141.
  15. Kim, S. D., Jang, K. H., Kim, J. K., 1998, Syntheses of new nitrogen-oxygen ligands and their stability constants of transition metal(II) ions, J. Kor. Chem. Soc., 42(5), 539-547
  16. Kim, S. D., Seol, J. M., 2011, Syntheses of pentadentate nitrogen-oxygen($N_{3}-O_{2}$) ligands with substituents and the determination of stability constants of their heavy metal(II) ions, J. Env. Sci. 20(6), 687-700. https://doi.org/10.5322/JES.2011.20.6.687
  17. Koseoglu, F., Kilic, E., Canel, E., Yilmaz, N., 1994, Protonation constants of some substituted salicylideneanilines in ethanol-water mixtures, Anal. Chim. Acta, 293, 87-94. https://doi.org/10.1016/0003-2670(94)00077-8
  18. Koseoglu, F., Kilic, E., Uysal, D., 1995, Protonation constants of some substituted 2-hydroxy-1- naphthalideneanilines in dioxan-water mixtures, Talanta, 42, 1875-1882. https://doi.org/10.1016/0039-9140(95)01649-X
  19. Lambert, J. B., Shurvell, H. F., Lighter, D. A., Cooks, R. G., 1987, Introduction to organic spectroscopy, Macmillan Publishing Company, New York, 247-311.
  20. Lee, N. H., Byun, J. B., Oh, T. H., 2005, Mn(III)-catalyzed oxidation of benzylic hydrocarbons using iodosobenzene as the oxidant, Bull. Kor. Chem Soc., 26(3), 455-456.
  21. Lin, H. K., Wang, X., Su, X., Zhu, S. R., Chen, Y. T., 2002, Synthesis and thermodynamic properties of novel tripod ligands and their cobalt(II), nikel (II), copper(II) and zinc(II) complex, Trans. Metal. Chem., 27, 384-389. https://doi.org/10.1023/A:1015051002413
  22. Martell, A. E., Motekaitis, R. J., 1992, Determination and use of stability constants. 2nd Ed. VCH, New York, 7-24
  23. Motekaitis, R. J., Martell, A. E., 1992, Stabilities of metal complexes of the meso and SS isomers of oxydisuccinic acid., Inorganic Chemistry, 31, 11-15. https://doi.org/10.1021/ic00027a004
  24. Parsons, G. H., Rochester, C. H., 1975, Acid ionization constants of 4-sub stitutes phenols in methanol+ water mixtures, J. Chem. Soc. Faraday, 71, 1058-1068. https://doi.org/10.1039/f29757101058
  25. Pillai, M. R. A., Barnes, C. L., Schlemper, E. O., 1994, Dinuclear complexes of rhenium(V) with aminephenol ligands: syntheses, characterize and x-ray crystal structures, Elsevier Science Ltd, 701-708.
  26. Rabie, U. M., Assran, A. S. A., Abou-El-Wafa, M. H. M., 2008, Unsymmetrical schiff bases functionalize as bibasic tetradentate (ONNO) and monobasic tridentate (NNO) ligands on complexation with some transition metal ions, J. Mole. Structure., 872, 113-122. https://doi.org/10.1016/j.molstruc.2007.02.023
  27. ymanpour, A., Hanifi, A., Kyanfar, A. H., 2008, Polymeric membrane and solid contact electrodes based on schiff base complexes of Co(III) for potentiometric determonation of perchlorate ions, Bull. Kor. Chem Soc., 29(9), 1774-1780. https://doi.org/10.5012/bkcs.2008.29.9.1774
  28. Walkwiak, W., Stewart, L. E., Lee, H. K., Szech, B. P., Bartsch, R. A., 1986, Competitive solvent extraction of alkaline-earth cations into chloroform by lipophlic acyclic diionzable polyethers, Anal. Chem., 58, 188-191. https://doi.org/10.1021/ac00292a045
  29. Yearwood, B., Parkin, S., Atwood, D. A., 2002, Synthesis and characterization of organotin schiff base chelates, Inorg. Chim. Acta., 333, 124-131. https://doi.org/10.1016/S0020-1693(02)00803-4